ES2293576T5 - Functional fluids containing alkylene oxide copolymers that have low pulmonary toxicity - Google Patents

Abstract

The invention relates to a method of reducing the inhalation toxicity of functional fluids by incorporating into a functional fluid an effective amount of copolymer which is obtainable by copolymerizing etheylene oxide, propylene oxide and/or butylenes oxide with an initiator monool or diol, said copolymer having a degree of unsaturation of less than about 0.01 meq/g.

Description

DESCRIPTION

Functional fluids containing alkylene oxide copolymers that have low pulmonary toxicity

The present invention relates to functional fluid formulations having low pulmonary toxicity, containing alkylene oxide copolymers having a low degree of unsaturation.

Copolymers with ethylene oxide and propylene oxide as starting monomers have been used for many years as base oils for the preparation of high performance lubricants.

The method used for the synthesis of these products is usually the anionic polymerization of ethylene oxide together with propylene oxide, starting from a mono- or difunctional alcoholate.

Functional fluids can be defined as fluids that provide multiple functions to meet the requirements of the given application. While an application may need emphasis on finding a function such as lubrication or heat transfer, functional fluids are expected to fulfill other application requirements as well including: force transmission, corrosion inhibition, electrical insulation, low pour point. , high viscosity index, minimal decomposing carbon dioxide, no staining, low color formation, oxidative and thermal stability, hydrolytic stability, low aquatic toxicity and biodegradability.

Polyalkylene glycols also known as polyglycols possess unique properties due to their high oxygen content. They are excellent lubricants that adsorb on metal surfaces. By varying the type of the monomer and / or the ratio of the monomers, its structure can be water-soluble or water-insoluble. They are the only lubricants that can be soluble in water.

Polyglycols were developed at the end of World War II and quickly found use in water-based hydraulic fluids that might not start a fire even when hydraulic lines were punctured by bullets or shrapnel grenades.

Many other applications were quickly identified including brake fluid, engine lubricants, rubber lubricants, and mold release. Random ethylene oxide and propylene oxide copolymers were found to be especially good base lubricants, more preferably the monoalkyl ether polymers.

The main advantages of these polyglycol copolymers as lubricants are their high viscosity index (ie low temperature dependence on viscosity), low viscosity at low temperatures, low coefficients of friction even without the addition of friction / antiwear additives, controlled setting the degree of water solubility of the copolymer through the choice of the ethylene oxide / propylene oxide ratio (characterized by high cloud points), non-corrosive and antistatic properties and very low pour points. Additionally, the thermal degradation of these polyglycol copolymers does not give any residue. Linear copolymers having a weight ratio of ethylene oxide to propylene oxide monomers in the range of 40:60 to 60:40 have proven particularly advantageous. These copolymers have, on the one hand, very low pour points, below -30 ° C, good solubility in water (cloud points greater than 50 ° C) and very high viscosity indices (greater than 250).

It is known from the literature (ECETOC, European Center for Ecotoxicology and Toxicology of Chemicals, Technical Report No. 55, Pulmonary Toxicity of Polyalkylene Glycols, Brussels, December 1997, ISSN-0773-8072-55) that some polyalkylene glycols show high acute pulmonary toxicity . Among these products are especially butanol initiated polyalkylene glycols containing ethylene oxide and propylene oxide in a weight ratio of about 50:50. Toxicity increases with increasing weight. Thus, for example, monobutoxyethylene oxide / propylene oxide copolymers containing ethylene oxide and propylene oxide in a 50:50 weight ratio exhibited, at a molecular weight of about 4000 g / mol, high toxicity. aerosol characterized by a low LC50 value of only 106 mg / m3. Also a random 50:50 EO / PO-polyether initiated diol having a molecular weight of 4000 g / mol showed a somewhat low LC50 value of 350 mg / m3. This high toxicity of the aerosol made it necessary for processors and users of these linear copolymers to take complicated technical measures, such as, for example, encapsulation of plants, to protect personnel from aerosols.

A tricky way to replace these products is to switch to a completely different chemistry. US 2001/0031855 teaches that polyol-initiated ethylene oxide / propylene oxide copolymers having a weight ratio of the central branch and an ethylene oxide / propylene oxide from 40:60 to 60:40, made from an alcohol having at least 4 OH groups, it has outstanding properties with respect to pour point, water solubility and viscosity index and at the same time is non-toxic on exposure to aerosols. For processors, this avoids complicated technical measures for plant encapsulation and to protect personnel from aerosols. However, the disadvantage of the products described in US2001 / 0031855 is that they require new formulations and that they do not always show satisfactory results in the applications when the products started by butanol are usually used.

It was therefore the object of the present invention to provide suitable alkylene oxide copolymers as base oils for lubricants which are initiated with the monool or diol initiators and yet have no toxicological potential in aerosol formation.

We found that this object is achieved by an alkylene oxide copolymer that is obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g. Copolymers in general show an LC50 value greater than 1000 mg / m3 (4 hours), determined according to method 403 of the OECD Guideline. The copolymers are preferably obtained in the presence of a DMC catalyst.

The present invention relates to functional fluids defined by the subject matter of the claims.

Also described in this document is a method of reducing the inhalation toxicity of functional fluids by incorporating into a functional fluid an effective amount of a copolymer obtained by copolymerization of ethylene oxide, propylene oxide and / or oxide. of butylene with a monool or diol initiator, said copolymer having a lower degree of unsaturation of about 0.01 meq / g.

The degree of unsaturation of the copolymers is preferably less than 0.008 meq / g, more preferably less than 0.005 meq / g. The degree of unsaturation is determined by measuring the iodine value (according to Kaufmann, DGF-C-V 116). The method gives the iodine value in g of I2 / 100 g polyether. A value of 1 g I2 / 100 g corresponds to 0.0394 mmol I2 / g = 0.0394 meq / g.

Preferred functional fluids are industrial lubricants, automobile lubricants, navigation lubricants, and aviation lubricants.

Copolymers having a lower degree of unsaturation of about 0.01 meq / g show particularly low pulmonary toxicity. The LC50 value of the copolymers is preferably greater than 1500 mg / m3, more preferably greater than 2000 mg / m3. The LC50 value of the copolymers can be as high as 5000 mg / m3 or even higher.

The LC50 value is determined by one of the following identical test methods: OECD Guideline method 403; U.S. EPA Guideline OPPTS 870.1300; EU Guideline 92/69 / EEC and 93/21 / EEC: "Acute Inhalation Toxicity Study in Wistar Rats" (with 4-hour exposure to a liquid aerosol).

The alkylene oxide copolymers can generally be incorporated into the functional fluid in an amount from 75 to 99% by weight, based on the total weight of the anhydrous functional fluid.

Alkylene oxide copolymers are started with a monool or diol as the initiator. The monool initiator is preferably a C1-C18 mono-alcohol or a polyoxyalkylene monoether of a C1-C18 mono-alcohol containing from 1 to 20 oxyalkylene units. Preferred oxyalkylene units are oxyethylene and / or oxypropylene units. The polyoxyalkylene monoether used as a monool initiator can be obtained by alkoxylation of the C1-C18 mono-alcohol in the presence of an alkaline catalyst, such as sodium or potassium hydroxide, acid catalyst, such as mineral acid, Lewis acid catalyst, such as boron trifluoride or DMC-catalyst, as described below, in a separate step prior to the copolymerization step.

Diols can also be used as initiators. Preferred examples are ethylene glycol, 1,2-propylene glycol, 1,2-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.

More preferably, the monool initiator is selected from the group consisting of n-butanol, iso-butanol, 2-ethyl hexanol, 2-propyl heptanol, butyl glycol, butyl diethylene glycol, butyl triethylene glycol, butyl propylene glycol, butyl dipropylene glycol, butyl tripropylene glycol, methyl diglycol. , methyl triglycol, methyldipropylene glycol, methyltripropylene glycol, methanol, ethanol, hexanol, isononanol, decanol, 2-butyloctanol, oleyl alcohol, octadecanol (for example stearyl alcohol), isononadecanol and C4-C8 alcohol mixtures are commonly used (degree of branching DOB < 0.1), C6-C10 alcohols (DOB <0.1), C10-C18 alcohols (DOB <0.1), C12-C16 alcohols (DOB <0.1), C12-C14 alcohols (DOB <0, 1), C16-C18 alcohols (DOB <0.1), C9-C11 alcohols (DOB <0.2), C12-C15 alcohols (DOB <0.2), C12-C13 alcohols (DOB 0.3-0 , 5), C11-C15 alcohols ^{(D or B} 0.3-0.5), C13-C15 alcohols (DOB 0.4-0.6), isotridekanols (DOB 1.3-1.7), C16 + alcohols - (DOB 1.5-2.0), isodecanols (DOB 2.0-2.5), isotridecanols (DOB 2.0-2.5) and isotridecanols (DOB 3.2-3.8). The degree of branching (DOB) is defined as the number of methyl groups per molecule minus 1. A strictly linear alcohol such as ethanol has one methyl group per molecule and therefore a degree of branching of 0. The degree of branching is can be determined by NMR-analysis.

A particularly preferred initiator is n-butanol.

The alkylene oxide copolymers can be block copolymers or random copolymers. Ethylene oxide / propylene oxide copolymers are preferred, ethylene oxide / random propylene oxide copolymers are particularly preferred. The oxyethylene / oxypropylene weight ratio is generally 10:90 to 90:10, preferably 25:75 to 75:25, and more preferably 40:60 to 60:40.

The copolymerization of ethylene oxide, propylene oxide and / or butylene oxide is preferably carried out in the presence of a DMC catalyst.

Suitable DMC catalysts prepared have for example the formula (I)

M ^1st [M ² (CN) ^b (TO) ^c ] ^d ■ fM ^{1 g} X ⁿ ■ h (H ² O) ■ eL (I),

where

M1 is a metal ion selected from the group consisting of Zn2 +, Fe2 +, Co3 +, Ni2 +, Mn2 +, Co2 +, Sn2 +, Pb2 +, Mo4 +, Mo6 +, Al3 +, V4 +, V5 +, Sr2 +, W4 +, W6 +, Cr2 +, Cr3 +, Cd2 +, Hg2 +, Pd2 +, Pt2 +, V2 +, Mg2 +, Ca2 +, Ba2 +, Cu2 +, M2 is a metal ion selected from the group consisting of Fe2 +, Fe3 +, Co2 +, Co3 +, Mn2 +, Mn3 +, V4 +, V5 +, Cr2 +, Cr3 +, Rh3 +, Ru2 +, Ir3 +,

and M1 and M2 are identical or different,

A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,

X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, and nitrate,

L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, and sulfides,

and

a, b, c, d, g and n are selected so that the compound is electrically neutral, and

e is the coordination number of the ligand, a fraction or integer greater than or equal to 0, f is a fraction or integer greater than or equal to 0, and

h is a fraction or integer greater than or equal to 0,

where the multimetallic cyanide compounds of the formula (I) are preferably crystalline.

Preference is given here to crystalline multimetallic cyanide compounds in which M1 is Zn (II) and M2 is Co (III). This preferred class of multimetallic cyanide compounds will hereinafter be referring to the zinc hexacyanocobaltates.

Within the class of zinc hexacyanocobaltates, there are in turn embodiments of formula (I) that are particularly preferred.

Particular preference is given to crystalline multimetallic cyanide compounds in which the anion X is formate, acetate or propionate and f is then greater than 0 and which have X-ray diffraction patterns as described in DE 197,42,978. Among these compounds, in turn preference is given to those in which the anion X is acetate and in particular to those that crystallize in a monoclinic crystal system.

Among these multimetallic cyanide compounds in which M1 is Zn (II), M2 is Co (III), and X is acetate and having a monoclinic crystal system, there are further preferred embodiments with respect to the morphology of the primary crystals. Preference is given to platelet-shaped multimetallic cyanide compounds, i.e. multimetallic cyanide compounds in which the length and width of the primary crystallites are at least three times as great as the thickness of the primary crystallites.

The preferred preparative process for the preparation of DMC catalysts comprises at least two steps: (a) precipitation of a multimetal cyanide phase, hereinafter referred to as the precursor phase, by reacting a metal salt with a cyanomethalate compound (step precipitation), and

(b) recrystallization of the multimetal cyanide precursor phase to convert it to the desired catalytically active multimetal cyanide phase, which hereafter will be referred to as a catalyst phase (recrystallization step).

A multimetal cyanide phase is a multimetal cyanide compound that has a particular crystalline structure.

The precipitation of the multimetal cyanide precursor phase is carried out, as described in the literature, by combining an aqueous solution of a metal salt M1gXn, where M1, X, g and n are as defined for formula I, with a aqueous cyanomethalate solution, comprising at least one cyanometalate compound of the formula Bx [M2 (CN) b (A) c] z, where B is an alkali metal, an alkaline earth metal and / or hydrogen, M2, A, b and c are as defined for formula I and x and z are numbers greater than zero. It is particularly preferred that B is a hydrogen, as described in EP 862,947.

Corresponding to the preferred phases of the multimetal cyanide catalyst, described above, the preferred metal salts are zinc carboxylates, in particular zinc formate, zinc acetate and zinc propionate.

Additionally, one or both of the aqueous solutions may, if desired, additionally comprise at least one organic ligand L selected from the classes of substances described above or as described in WO 98 / 16,310, page 6, lines 13-26, and / or at least one surfactant substance. The surfactant compounds used can be, in particular, anionic, cationic, non-ionic and / or polymeric surfactants.

In particular, use is made of non-ionic and / or polymeric surfactants. Among this group, preference is particularly given to fatty alcohol alkoxylates, block copolymers of various epoxides having different hydrophilicity, castor oil alkoxylates or block copolymers of epoxides and other monomers, for example acrylic acid or methacrylic acid. The substances used must have a moderate to good solubility in water.

Fatty alcohol alkoxylates can be prepared by reacting a fatty alcohol, preferably one having 8-36 carbon atoms, in particular 10-18 carbon atoms, with ethylene oxide, propylene oxide and / or butylene oxide. . The polyether part of the alkoxylate of the fatty alcohol may consist of pure polyethers of ethylene oxide, propylene oxide or butylene oxide. Copolymers of two or three different alkylene oxides or block copolymers of two or three different alkylene oxides are also possible. Fatty alcohol alkoxylates having pure polyether chains are, for example, the products Lutensol® AO and Lutensol® TO from BASF AG. Fatty alcohol alkoxylates having block copolymers as polyether part are Plurafac® LF products from BASF AG. Particularly preferred polyether chains consist of 2 to 50, in particular 3-15, alkylene oxide units.

Surfactant block copolymers comprise two different polyether blocks having different hydrophilicities. Block copolymers that can be contained in ethylene oxide and propylene oxide (Pluronic® products, BASF AG). The solubility in water is controlled via the lengths of the various blocks. The molar masses of these compounds are usually in the range from 500 Da to 20,000 Da, preferably from 1000 Da to 6000 Da and in particular 1500-4000 Da. In the case of ethylene oxide / propylene oxide copolymers, the ethylene oxide content is 5 to 50% by weight and the propylene oxide content is 50 to 95% by weight.

Copolymers of alkylene oxide with other monomers preferably have ethylene oxide blocks. Other monomers can be, for example, butyl methacrylate (PBMA / PEO BE1010 / BE1030, Th. Goldschmidt), methyl methacrylate (Pm MA / PEO ME1010 / ME1030, Th. Goldschmidt) or methacrylic acid (EA-3007, Th. Goldschmidt) .

Surfactant compounds are generally not incorporated into the framework of multimetallic cyanide compounds nor do they bind in the form of a complex and can be washed off after the multimetallic cyanide compounds have been prepared.

The aqueous cyanomethalate solution preferably has a content of M2 from 0.1 g / l to 100 g / l, preferably from 1 g / l to 20 g / l, particularly preferred from 5 g / l to 15 g / l.

The M1 content of the metal salt solution is 0.1% by weight to 10% by weight, preferably 1% by weight to 5% by weight, based on the mass of the metal salt solution.

In a preferred embodiment of the preparative process, the precipitation step is carried out initially by charging the cyanometalate solution and adding the metal salt solution. The amount of metal salt solution is selected so that the multimetal cyanide precursor phase can be produced.

The temperature in the precipitation stage is preferably in the range of 20 to 95 ° C, in particular 35 to 80 ° C. The metal salt solution is preferably measured over a period of 5 minutes to 5 hours, in particular 30 minutes to 3 hours.

The ratio of M1: M2 in the precipitation step is, depending on the desired parent compound, from 1: 1 to 3: 1. In the preparation of multimetallic cyanide compounds in which M1 is Zn (II), M2 is Co (III), and X is formate, acetate or propionate, preferably those in which X is acetate and which have a crystal system monoclinic, a crystallization phase of zinc hexacyanocobaltate in a cubic crystal system is precipitated in a precipitation stage. In this case, the M1: M2 ratio is preferably 1.5: 1.

The currently desired multimetal cyanide catalyst phase is then produced in the second stage of the process as described above, also referred to as the recrystallization stage. The recrystallization stage can immediately follow the first stage of the process, namely the precipitation stage. However, the precipitation and recrystallization steps can also be separated from each other in space and / or time.

In the recrystallization step, the multimetal cyanide precursor phase prepared in the precipitation step is recrystallized to form the multimetal cyanide compound having the desired crystal structure by setting the appropriate conditions.

The phases of the multimetallic cyanide compounds that occur after the first stage or the second stage naturally have to differ in at least one measurable property, for example composition, X-ray diffraction pattern, morphology, particle size or agglomeration.

To adjust the appropriate conditions for recrystallization, alterations were made, for example, in the temperature and / or the pH of the precipitation of the suspension and / or the M1: M2 ratio (by adding the metal salt solution and / or cyanometalate solution). Changes in the M1: M2 ratio can also lead to changes in the absolute concentration of M1 and M2. The solutions added to change the M1: M2 ratio can also contain water-miscible substances such as L-ligands and / or surface-active substances. Furthermore, additional water-miscible substances such as L-ligands and / or surface-active substances can be added between the precipitation stage and the recrystallization stage.

In a further embodiment, it is possible to separate the multimetal cyanide precursor phase from the precipitation suspension and resuspend the resulting solid for recrystallization.

Additionally, the metal salt solutions used in precipitation and recrystallization do not have to be the same. They may differ in either the concentration of the metal salt, or the possible addition of the L ligands and / or surfactant. This applies equally to the cyanometalate solution. In this embodiment of the process, it is possible for the metals in the multimetal cyanide compound to be partially exchanged.

In recrystallization, either the compound from the precipitation step is resuspended in water and initially charged and, if a change in the M1: M2 ratio is necessary for recrystallization, the appropriate amount of the metal salt solution or the solution cyanometalate is added, or the metal salt solution or cyanometalate solution is initially charged and the liquid dispersed multimetallic cyanide precursor phase is added. The addition can take from 2 minutes to 5 hours, preferably 15 minutes to 2 hours.

The temperatures used in the recrystallization are in the range of 20 ° C to 95 ° C, preferably 40 ° C to 90 ° C. The temperature in recrystallization is generally different from the temperature in precipitation. However, both the precipitation and recrystallization should be carried out at the same temperature, this is preferred for process engineering reasons.

The M1: M2 ratio in recrystallization can be 1:10 to 10: 1, but is preferably 1.5: 1 to 3: 1.

In the case of the preparation of the preferred phases of the multimetallic cyanide catalyst in which M1 is Zn (II), M2 is Co (III), and X is acetate and which have a monoclinic crystal structure and are produced by recrystallization of a cubic precursor phase, the M1: M2 ratio in recrystallization is greater than 1.9: 1 and preferably in the range of 2: 1 to 3: 1. In this case, zinc acetate is used as the metal salt.

In order to obtain the primary crystallites of this preferred platelet-shaped multimetal cyanide catalyst phase, fatty alcohol alkoxylates, preferably fatty alcohol ethoxylates, or ethylene oxide / propylene oxide block copolymers are preferably added as substances. surfactants. Surface active substances can be added either in the precipitation stage or in the recrystallization stage. The surface-active substances are preferably added after the precipitation step and before the recrystallization step.

The course of recrystallization can, if macroscopically measurable parameters change, be followed by means of measurements. Such parameters can be the pH or the surface area of the solid. The change in the surface area of the solid can be followed by scattering of light.

The multimetal cyanide catalysts prepared can have a very low degree of agglomeration. 90% of the particles have a particle size (which can be determined by scattering laser light) in the range of 0.1 | jm to 100 | jm, preferably in the range of 0.1 | jm to 30 | jm, it is particularly preferred from 0.1 | jm to 20 | jm. The catalyst may have an X50 value of the measured particle size distribution of less than 20 µm, preferably less than 15 µm, in particular less than 10 µm.

Random alkylene oxide copolymers can be prepared initially by charging a stirred reactor with the monool initiator and DMC catalyst and dispersing the catalyst in the initiator. The contents of the reactor are preferably dried at elevated temperature and the reactor is purged with an inert gas hereinafter. The alkylene oxides, preferably ethylene oxide and propylene oxide are then added in parallel at a temperature of preferably 110 to 150 ° C. After the addition of the alkylene oxides is completed, the reaction is preferably continued until constant pressure is reached. The reaction mixture is cooled, the reactor is purged with nitrogen, and finally emptied. The catalyst can be removed from the product by filtration or the catalyst can remain in the product. To remove the catalyst, the product can be diluted with a solvent, such as toluene, acetone, or ethyl acetate, and the solvent evaporates after the catalyst has been completely filtered.

The initial reactor charge can also be a suspension of the catalyst in a solvent, such as toluene, or a suspension of the catalyst and the monool or diol initiator in a solvent. During the addition of some amount of the alkylene oxides, usually 40 to 95%, the monool or diol initiator can be added in parallel.

Preferred copolymers have a viscosity at 50 ° C of more than 20 mm2 / s, preferably more than 80 mm2 / s, more preferably 80 to 2500 mm2 / s, determined according to DIN 51562. A viscosity index is also preferred greater than 200, determined in accordance with ASTM D2270-74. In another preferred embodiment, these copolymers have a pour point, determined according to DIN 51597, lower than -30 ° C. Preferred copolymers have an average molecular weight Mw greater than 800 g / mol, more preferably greater than 2300 g / mol, it is particularly preferred from 2300 to 20000 g / mol.

Alkylene oxide copolymers are used in functional fluid formulations according to the invention. Alkylene oxide copolymers in particular are used in functional fluid formulations according to the invention to reduce the inhalation toxicity of functional fluid formulations.

In general, functional fluids can be industrial lubricants, automobile lubricants, navigation lubricants and aviation lubricants, in particular lubricants for the production of fibers, hydraulic fluids, gear oils, compressor fluids, turbine oils, metallurgical fluids , greases, bearing lubricants, wire lubricants and motor oils, quenching agent fluids and lubricants for fiber production, anhydrous hydraulic fluids, water glycol hydraulic fluids, metallurgical fluids, gear lubricants, compressor lubricants, lubricants coolant, mill and calender lubricants, brake fluids, 4-stroke engine oils, 2-stroke engine lubricants, mandrel or mold release lubricants for the rubber-based elastomer process, lubricating greases and transmission lubricants universal.

For example, lubricants with low inhalation toxicity for fiber production may contain

a) 65-95% by weight of the copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g ;

b) 3-20% by weight of emulsifiers, such as fatty alcohol alkoxylates, castor oil ethoxylates or fatty amine ethoxylates;

c) 0-5% by weight of antistatic agents, such as sulfates, sulfonates or betaines;

d) 0-5% by weight of corrosion inhibitors, such as oleyl phosphonates or sarcosinate;

e) 0-5% by weight of other additives, such as stabilizers, antioxidants, biocides or wetting agents.

For example, lubricants with low inhalation toxicity for fiber production may contain components c) -e) in an amount of at least 0.01% by weight of each.

The formulation is diluted with water, so the final aqueous formulation contains 10% to 90% water.

Hydraulic fluids with low inhalation toxicity are described herein as containing the copolymers described above, which have a low degree of unsaturation.

Hydraulic systems are used frequently in all aspects of daily life. Polyakylene glycols, preferably butanol initiated EO / PO random copolymers are used as bases and components in hydraulic fluids due to their excellent lubrication properties. As a class of polymer, they are more fire resistant than mineral oil fluids and are used most especially in fire resistant hydraulic fluid formulations in industries where constant sources of ignition occur such as steel fabrication and die casting. aluminum.

Preferred anhydrous hydraulic fluids with low inhalation toxicity contain

a) 75-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants, such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0 - 5 % by weight preferably 0.5 - 2 % by weight of corrosion inhibitors such as organic acids and esters of these, compounds containing nitrogen-, phosphorus-, and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, alkyl and aryl phosphites;

e) 0-5% by weight preferably 0.3-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

f) 0-5% by weight preferably 0.2-2% by weight of other additives such as dispersants, seal bulking enhancers, antifoams, stabilizers and pigments.

Preferred low inhalation toxicity water glycol hydraulic fluids contain

a) 30-60% by weight preferably 35-50% by weight of a copolymer obtained by copolymerizing ethylene and oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of unsaturation lower about 0.01 meq / g;

b) 0-40% by weight preferably 0-20% by weight of glycols such as ethylene glycol, diethylene glycol and propylene glycol; c) 20-45% by weight preferably 25-40% by weight of water;

d) 0-15% by weight preferably 2-10% by weight of thickening polyalkene such as trimethylolpropane-initiated trimethylolpropane-initiated heteric polymer of trimethylolpropane oxide;

e) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

f) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

g) 0 - 5% by weight preferably 0.5 - 2% by weight of corrosion inhibitors such as organic acids and esters of these, compounds containing nitrogen-, phosphorus-, and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid and alkyl amines;

h) 0-5% by weight preferably 0.8-3% by weight of limit lubricants such as carboxylic acids and fatty amines;

i) 0-5% by weight preferably 0.2-1% by weight of other additives such as defoamers and pigments. The invention further relates to metallurgical fluids containing the above-described copolymers having a low degree of unsaturation.

Polyakylene glycols, preferably butanol initiated EO / PO random copolymers have been used successfully as the base fluids for water soluble metal cutting and milling fluids. They have also been used as lubricants in molding operations such as stamping, rolling, and illustration. Metallurgy operations have an advantage of a unique property of polyalkylene glycols which is reverse solubility. This means that the polymer becomes less soluble in water as the temperature of the solution increases. When the polyalkenglycol polymer comes into contact with hot metal, it comes out of solution and covers the metal part with a concentrated film that provides excellent lubricity.

The invention relates to a functional fluid comprising

a) 25-55% by weight preferably 30-45% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 35-65% by weight preferably 45-60% by weight of water;

c) 5-26% by weight preferably 10-20% by weight of the metal passivators and corrosion inhibitors such as tolyltriazole, benzotriazole, organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, phosphites of alkyl and aryl;

d) 0-5% by weight preferably 0.2-1% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols such as butylated hydroxytoluene;

e) 0-5% by weight preferably 0.3-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, alkyl and aryl phosphates and carboxylic acids;

f) 0-5% by weight preferably 0.5-2% by weight of other additives such as dispersants, antifoams and stabilizers,

wherein the functional fluid is a water soluble metallurgical fluid of low inhalation toxicity.

Low inhalation toxicity gear lubricants containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

Proper gear lubrication is integral to proper transmission maintenance. Polyakylene glycols, preferably butanol initiated EO / PO random copolymers when formulated with necessary additives provide very good lubrication service life, stability and transmission. Due to their wide viscosity range, butanol initiated EO / PO random copolymer based formulations have been used successfully in helical gear, herringbone, bevel, spiral bevel, spur and serpentine applications.

Preferred gear lubricants with low inhalation toxicity contain

a) 75-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0 - 5% by weight preferably 0.5 - 2% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus-, and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, alkyl and aryl phosphites;

e) 0-5% by weight preferably 0.2-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

f) 0-5% by weight preferably 0.5-2% by weight of other additives including dispersants, antifoam agents and stabilizers.

The invention further relates to compressor lubricants with low inhalation toxicity containing the above-described copolymers having a low degree of unsaturation.

Polyakylene glycols, preferably butanol initiated EO / PO random copolymers are used as base fluids for formulated compressor lubricants. Due to their high temperature stability, lubricity, and resistance to sludge, these formulations are used in centrifugal, reciprocating, fin and rotary screw compressors for applications including helium, hydrogen, nitrogen, carbon dioxide, natural gas, and ethylene.

The invention relates to a functional fluid comprising

a) 75-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols such as dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0-5% by weight of corrosion inhibitors such as organic acids, esters thereof, nitrogen-, phosphor-, and sulfur-containing compounds, derivatives of succinic acid, 4-nonylphenoxyacetic acid, alkyl and aryl phosphites;

e) 0-5% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

f) 0 - 5% by weight of other additives such as dispersants, antifoam additives including polydimethylsiloxanes and polyalkylene glycols, and stabilizers,

wherein the functional fluid is a low inhalation toxicity compressor lubricant.

Preferably, the low inhalation toxicity compressor lubricants of the invention contain components d) -f) in an amount of at least 0.01% by weight each.

Low inhalation toxicity refrigeration lubricants containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

The Montreal Protocol in 1987 initiated the phase-out of the use of chlorofluorocarbons due to their harmful effect on the earth's ozone layer. In mobile air conditioning refrigerant R-134a was chosen as a non-ozone depleting replacement. In mobile air conditioning units the lubricant travels through the system with the refrigerant. Butanol initiated EO / PO random copolymers are soluble in R-134a and are widely used as the base for mobile air conditioning lubricants due to this excellent solubility and lubricity.

Preferred refrigeration lubricants with low inhalation toxicity contain

a) 75-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols including dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene and phenothiadine;

d) 0 - 5% by weight preferably 0.5 - 2% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, phosphites alkyl and aryl;

e) 0-5% by weight preferably 0.2-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates, for example tricreasyl phosphate;

f) 0-2% by weight preferably 0.1-0.5% by weight of antifoam additives such as polydimethylsiloxanes and polyalkylene glycols;

g) 0-5% by weight preferably 1-3% by weight of stabilizers such as neopropylene glycol diglycidylether, polypropylene glycol diglycidylether, phenyl glycidylether and cycloaliphatic epoxy compounds;

h) 0-5% by weight preferably 2-4% by weight of other additives such as viscosity index enhancers, pour point reducing agents, detergents and dispersants.

Low toxicity calender and mill lubricants containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

Large mills and calenders are used in the textile, rubber, paper and plastic industries, which require lubrication of anti-friction bearings and bearings. These lubricants must operate at high temperatures of> 150 ° C. Polyakylene glycols, preferably butanol initiated EO / PO random copolymers form volatile chemicals when thermally decomposed and do not form carbonaceous residues like mineral oils that can inhibit proper lubricant performance.

Preferred mill and calendra lubricants with low toxicity contain

a) 75-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example as dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0 - 5% by weight preferably 0.5 - 2% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, phosphites alkyl and aryl;

e) 0-5% by weight preferably 0.2-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

f) 0-5 % by weight preferably 1-4 % by weight of other additives including dispersants, antifoams, stabilizers, viscosity index enhancers and detergents.

Disclosed herein are DOT 3 brake fluids with low inhalation toxicity containing the above-described copolymers having a low degree of unsaturation.

Polyakylene glycols, preferably butanol initiated EO / PO random copolymers are suitable base fluids for DOT 3 brake formulations due to their lubricity, thermal and oxidative stability.

Preferred DOT 3 brake fluids with low inhalation toxicity contain

a) 50-99% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g;

b) 0-30% by weight of glycol ethers such as methyl triethylene glycol ether and butyl triethylene glycol ether;

c) 0-20% by weight of glycols such as triethylene glycol;

d) 0-5% by weight of metal passivators; such as tolyltriazole, benzothiazole, and benzotriazole;

e) 0-5% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

f) 0-5% by weight of corrosion inhibitors such as organic acids, esters of these, nitrogen-, phosphorus- and sulfur-containing compounds, derivatives of succinic acid, 4-nonylphenoxyacetic acid, alkyl and aryl phosphites;

g) 0-5% by weight of antiwear and extreme pressure additives, such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

h) 0-5% by weight of other additives such as defoamers, viscosity index enhancers, pour point reducing agents, detergents and dispersants.

Preferably, DOT 3 brake fluids with low inhalation toxicity contain components b) -h) in an amount of at least 0.01% by weight of each.

Low inhalation toxicity 4-stroke engine oils containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

Polyakylene glycols, preferably butanol-initiated EO / PO random copolymers can be used as base fluids in 4-stroke engine lubricant formulations that offer the finishing lubricant of excellent lubricity, thermal and oxidative stability, and resistance to sludge formation. and carbonaceous residues such as mineral oil fluids do at high operating temperatures. Formulations based on such polymers also show better lubricity than synthetic motor oils based on polyalphaolefin.

Preferred 4-stroke engine oils with low inhalation toxicity contain

a) 85-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0 - 5% by weight preferably 0.5 - 2% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, phosphites of alkyl and of aryl and alkyl amines;

e) 0-5% by weight preferably 0.5-3% by weight of detergents such as calcium and magnesium sulphonates, salicylate;

f) 0-5% by weight preferably 0.3-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

g) 0-5 % by weight preferably 0.5-3 % by weight of other additives such as dispersants, antifoam additives, friction modifiers and anti-fogging agents.

Low inhalation toxicity 2-cycle motor lubricants containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

Formulations based on polyalkylene glycols, preferably butanol initiated EO / PO random copolymers are well suited to cold air lubrication of two-stroke cycle engines. The clean burn characteristic of these polyalkenyl glycol polymers greatly reduces problems related to combustion chamber deposits, and spark plug greasing. Polyakylene glycols, preferably butanol initiated EO / PO random copolymer polymers are completely miscible with methanol and methanol / nitromethane mixtures.

Preferred 2-cycle engine lubricants with low inhalation toxicity contain

a) 85-98% by weight preferably 90-97% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 0.2-1% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight preferably 0.5-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0 - 5% by weight preferably 0.5 - 2% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, phosphites of alkyl and of aryl and alkyl amines;

e) 0-5% by weight preferably 0.5-3% by weight of detergents such as calcium and magnesium sulphonates, salicylate;

f) 0-5% by weight preferably 0.3-2% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

g) 0-5% by weight preferably 0.5-3% by weight of other additives such as dispersants, antifoam additives, friction modifiers and anti-fogging agents.

Low inhalation toxicity mold or mandrel release lubricants containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

Polyglycols have minimal swelling effects in most natural and synthetic rubbers. For this reason and their excellent lubricity, polyglycols are ideal bases for mandrel and rubber lubricants as well as mold release lubricants. In many cases the lubricant is diluted with water or some other water soluble solvent. Its inverse solubility can be used in aqueous systems to recover polymer recovery for reuse.

Preferred mandrel or mold release lubricants with low inhalation toxicity for the rubber-based elastomer process contain

a) 90-99% by weight preferably 94-98% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 0-5% by weight preferably 1-3% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example Nn-butyl-para-aminophenol, N, N'-dimethyl-para-phenylenediamine, phenothiazine and butylated hydroxytoluene ;

c) 0-5% by weight preferably 1-3% by weight of other additives such as defoamers, detergents and stabilizers.

The invention further relates to quenching agent fluids with low inhalation toxicity, containing the above-described copolymers having a low degree of unsaturation.

Quenching agents are used to impart specific properties to metal parts, particularly steel. The two most common quenching agents are water and mineral oil however for many applications they cool the metal very fast or very slow respectively. Mineral oil has additional disadvantages of limited variability in quenching rates, smoke emissions, flammability, and disposal problems. The Synthetic polymer quenching agents can be formulated to give a wide range of quench rates intermediate between water and mineral oil. Polyalkylene glycol based quenching formulations are the most widely used polymer quenching agents due to their quenching performance providing reduced cracking and residual stress and are also fire resistant.

The invention further relates to a functional fluid comprising

a) 5-35% by weight preferably 5-15% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a degree of lower unsaturation of about 0.01 meq / g;

b) 65-95% by weight preferably 82-94.5% by weight of water;

c) 0-5% by weight preferably 0.1-1% by weight of corrosion inhibitors such as organic acids, alkyl amines, esters of these, nitrogen-, phosphorus- and sulfur-containing compounds, and derivatives of succinic acid; d) 0-5% by weight preferably 0.1-1% by weight of other additives such as dispersants, antifoams and stabilizers.

wherein the functional fluid is a low inhalation toxicity quenching agent.

Low inhalation toxicity lubricating greases containing the above-described copolymers having a low degree of unsaturation are disclosed herein.

Greases are used in applications where the lubricant must be retained in the area of need and the specificity of the application makes this impossible or impractical for liquid lubricants. Other advantages of greases include: no spatter, less frequent applications, less expensive seals can be used, easier to handle, adhere better to surfaces, and can reduce noise and vibration. Polyglycols can be used to produce excellent conventional fats but also specialty fats that take advantage of the unique properties of polyglycols including a water soluble fat or a fat that is resistant to mineral oil.

Preferred lubricating greases with low inhalation toxicity contain

a) 40-85% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g;

b) 0-45% by weight of the butanol initiated polypropylene glycol;

c) 5-15% by weight of thickeners such as lithium, calcium and sodium soaps, complex soaps, and treated bentonite - highly dispersed aluminosilicate clay and silicic acid;

d) 0-5% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

e) 0-5% by weight of antioxidants, including organic amines and hindered phenols;

f) 0-5% by weight of corrosion inhibitors such as disodium sebacate, alkenylsuccinic acid esters, imidazoline and sarcosine derivatives, sodium and calcium sulfonates;

g) 0-5% by weight of antiwear and extreme pressure additives such as dithiophosphates, dithiocarbamates and thiadiazole derivatives;

h) 0-5% by weight of other additives such as solid lubricants and tackifiers.

Preferably, lubricating greases with low inhalation toxicity contain components b) - and d) -h) in an amount of at least 0.01% by weight of each.

Disclosed herein are universally transmissible lubricants with low inhalation toxicity containing the above-described copolymers having the specific low degree of unsaturation.

Special multipurpose lubricants used in agricultural and work machines are called universal tractor transmission oils (UTTOs) as they function from a single container such as transmission and brake fluid. Polyglycols are excellent bases for such fluids due to their low pour points and high viscosity index. The use of the water soluble polyglycol base would also have low aquatic toxicity and be biodegradable. Preferred universal transmission lubricants with low inhalation toxicity contain

a) 85-98% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g;

b) 0-5 % by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole;

c) 0-5% by weight of antioxidants, including dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene;

d) 0 - 5% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, alkyl and aryl and alkyl phosphates amines;

e) 0-5% by weight detergents such as calcium and magnesium sulphonates, salicylate;

f) 0-5% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates;

g) 0 - 5% by weight of other additives such as dispersants, antifoam additives, friction modifiers and antifog agents.

Preferably, universal transmission lubricants with low inhalation toxicity contain components b) -g) in an amount of at least 0.01% by weight of each.

Additionally, the alkylene oxide copolymers described above can be used for the production of polyether siloxanes. For this purpose the alkylene oxide copolymer (A),

R-O- (AO) n-H (A)

where

R represents a saturated residue of a monoalcohol initiator from which a hydroxyl group is removed,

(AO) n represents a polyoxyalkylene group formed by the copolymerization of alkylene oxides as described above,

n represents a number from 1 to 200,

is reacted with a polysiloxane (B)

R'1-O- (MeSiH) ^m -O- (Me ² Yes) ^or -O-R'2 (B)

where

R'1 and R'2 are independently any of the groups Me3Si, Me2SiH, MeSiH2 or SiH3,

m and n are independently of each other a number from 0 to 200, provided that m can be 0 only if at least one of the other SiH bond is present in the polysiloxane,

or a polysiloxane (C)

R "1 -O- (MeSiCl) ^m -O- (Me ² Yes) ^or -O-R "2 (C)

where

R "1 and R" 2 are independently any of the groups Me3Si, Me2SiCl, MeSiCh or SiCl3,

m and n are independently of each other a number from 0 to 200, provided that m can be 0 if at least one of the other SiCl bond is present in the polysiloxane,

to give the polyether siloxane (D)

R '”1-O- (MeSi - [(AO) ⁿ O-R]) m-O- (Me ² Yes) ^or -O-R '”2 (D)

where

R '”1 and R'” 2 are independently any of the groups Me3Si, Me2Si - [(AO) n-O-R], MeSi - [(AO) n-O-R] 2 or Si - [(AO) n-O-R] 3

m and n are independently a number from 0 to 200, provided that m can only be 0, if at least one of the other group Si - [(AO) n-O-R] is present in the polysiloxane.

The resulting polyether siloxane D can be used as a pairing agent in covers or as a foam stabilizer in PUfoam, as described in DE 198 16 921; J. Henning, F. Müller, J. Peggau, "Silicontenside - Multitalent mit Rückgrat", SOFW-Journal, 127. Jahrgang 1 / 2-2001, p. 38 ff; Bryant, Stewart, J. Cell. Plast., 1973, 9, p. 99-102; and US 2,846,458.

The invention is illustrated by the following examples:

Examples

Example 1

Preparation of a DMC catalyst (according to WO 01/64772)

1724 g of aqueous hexacyanocobaltic acid (cobalt content (9 g / l, Pluronic® PE 6200 content: 1.2% by weight) were placed in a 3 I shaking vessel equipped with a Hoesch stirrer, a pH probe and a light dispersion probe and were heated while stirring to 60 ° C. Subsequently, while stirring at a stirring force of 1 W / I, 1464 g of aqueous solution of zinc acetate dihydrate (Zinc content: 2.6% by weight , content of Pluronic® PE 6200 (BASF AG): 1.2% by weight based on the zinc acetate solution) which has also been heated to 60 ° C were fed for a period of 20 minutes. X from a sample taken at the end of the measured addition, showed that the obtained multimetal cyanide compound had a cubic structure.

The suspension of the precipitation thus obtained was then stirred at 60 ° C for another 60 minutes. During this time, the pH dropped from 4.0 to 3.4. The solid was subsequently completely filtered and washed on the filter with 12 times the volume of water cake.

The X50 value of the particle size determined in the precipitation suspension by means of the scattering of laser light was 7 µm.

The wet filter cake had a multimetal cyanide content of 20.8% by weight. The X-ray diffraction pattern of the solid obtained in this way could be cataloged according to the monoclinic crystal system. The particle habit was platelet-like and the primary particles only agglomerated weakly.

Example 2

250 g of 1-butanol and 4.1 g of KOtBu were loaded into an autoclave and carefully purged with nitrogen five times. The reaction mixture was heated to 130 ° C and a mixture of 550 g of ethylene oxide and 550 g of propylene oxide was added at this temperature within 16 hours. The volatile components are evaporated and the product is finished by treatment with Amberlite IR-120 (Fluka) and ion exchanger filtration. 1.2 kg of a slightly yellowish oil with an OH number of 141 mg KOH / g were obtained.

Example 3

310 g of butyl oligoalkylene glycol from Example 2 and 680 mg of DMC catalyst from Example 1 were heated at 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated to 130 ° C. After reaching 130 ° C in 15 h, 1205 g of propylene oxide and 1205 g of ethylene oxide were added in parallel with stirring. After the addition of the oxides was completed, the reaction mixture was stirred at 130 ° C for one hour, then cooled to 80 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca. 2.8 kg of the product. The product was diluted in ethyl acetate, the catalyst was filtered off and the solvent was evaporated.

Analytical data:

OH-number determined according to DIN 53240: 15 mg KOH / g

Kinetic viscosity at 38 ° C: 455 mm2 / s

Degree of unsaturation: <0.1 g h / 100 g (according to Kaufmann, DGF-C-V 116); <0.004 meq / g

Example 4

570 g of butyl dipropylene glycol and 518 mg of the DMC catalyst from example 1 were heated at 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated to 130 ° C. After reaching 130 ° C, a mixture of 702 g of propylene oxide and 798 g of ethylene oxide was added within 22 h with stirring. After the addition of the oxides was completed, the reaction mixture was stirred at 130 ° C for one hour, then cooled to 80 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca. 2.0 kg of product, which was used in Example 5 without additional preparation.

Example 5

393 g of product from Example 1 and 727 mg of DMC catalyst from Example 1 were heated at 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated at 130 ° C. After reaching 130 ° C, a mixture of 1308 g of ethylene oxide and 1599 g of propylene oxide was added in 5 h with stirring. After the addition of the oxides was completed, the reaction mixture was stirred at 130 ° C for one hour, then cooled to 80 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca. 3.2 kg of product.

Analytical data:

OH-number determined according to DIN 53240: 9.3 mg KOH / g

Water content determined according to DIN 51777: 0.02%

Color determined according to DIN ISO 6271: 48 APHA

Conductivity determined according to DIN ISO 7888: 17 PS / cm

pH of 10% by weight of the solution in water: 6.5

Molecular weight determined by means of GPC: approximately 6000 g / mol

Dynamic viscosity at 23 ° C: 2485 mPas

Kinetic viscosity at 23 ° C, determined according to DIN51562: 2393 mm2 / s

Kinetic viscosity at 37.8 ° C, determined according to DIN51562: 942 mm2 / s

Degree of unsaturation: <0.1 g I2 / 100g (according to Kaufmann, DGF-C-V 116); <0.004 meq / g

LC50 value determined according to OECD Guideline Method 403:> 2.31 mg / L

Example 6

65 g of 2-ethyl hexanol and 218 mg of the DMC catalyst from example 1 were heated at 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated to 130 ° C. After reaching 130 ° C, a mixture of 750 g of ethylene oxide and 735 g of propylene oxide was added over 3.5 h with stirring. After the addition of the oxides was completed, the reaction mixture was stirred at 130 ° C for one hour, then cooled to 80 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca. 1.5 kg of the product.

Analytical data

OH-number determined according to DIN 53240: 17 mg KOH / g

Kinetic viscosity at 38 ° C: 377 mm2 / s

Degree of unsaturation: 0.03 g I2 / 100g (according to Kaufmann, DGF-C-V 116); 0.001 meq / g

Example 7

81 g of butyl diglycol and 90 mg of the DMC catalyst from example 1 were heated at 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated to 130 ° C. After reaching 130 ° C, a mixture of 410 g of ethylene oxide and 410 g of propylene oxide was added in 22 h with stirring. After the addition of the oxides was completed, the reaction mixture was stirred at 130 ° C for one hour, then cooled to 80 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca. 0.9 kg of the product.

Analytical data:

OH-number determined according to DIN 53240: 33 mg KOH / g

Kinetic viscosity at 38 ° C: 146 mm2 / s

Degree of unsaturation: 0.01 g I2 / 100g (according to Kaufmann, DGF-C-V 116); 0.0004 meq / g

Example 8

Pluriol® P 900, which is a 900 molecular weight polypropylene glycol obtained by alkaline catalysis, was used as an initiator for this synthesis.

900 g of Pluriol P 900 and 836 mg of the DMC catalyst from example 1 were heated at 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated to 140 ° C. After reaching 140 ° C, a mixture of 1167 g of propylene oxide and 1277 g of ethylene oxide was added in 15 h with shaking. After the addition of the oxides was completed, the reaction mixture was stirred at 140 ° C for one hour, then cooled to 100 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca. 3.3 kg of the product, which was used in example 9 below without further preparation.

Example 9

1672 g of the product of example 8 and 306 mg of the DMC catalyst of example 1 were heated to 100 ° C at a pressure of 20 mbar for two hours in an autoclave. The reaction mixture was purged with nitrogen three times and then heated to 140 ° C. After reaching 140 ° C, a mixture of 638 g of ethylene oxide and 584 g of propylene oxide was added within 3 h with stirring. After the addition of the oxides was completed, the reaction mixture was stirred at 140 ° C for one hour, then cooled to 100 ° C, purged with nitrogen and finally evacuated at 20 mbar to produce ca.

2.9 kg of the product. The product was filtered at 70-80 ° C to remove the catalyst.

Analytical data:

Product appearance: transparent colorless liquid

Solubility in water: free of particles

OH-number determined according to DIN 53240: 18.8 mg KOH / g

Water content determined according to DIN 51777: 0.1%

pH of 10% by weight of the solution in water: 6.2

Molecular weight determined by means of GPC: ca. 6000 g / mol

Kinetic viscosity at 25 ° C determined according to DIN 51562: 2560 mm2 / s

Dynamic viscosity at 20 ° C: 3100 mPas

Dynamic viscosity at 100 ° C: 170 mPas

Degree of unsaturation: 0.1 g I2 / 100 g (according to Kaufmann, DGF-C-V 116); 0.004 meq / g

Reference Example 10

A final stirring formulation is prepared by mixing:

93% by weight of the ethylene oxide / propylene oxide copolymer of Example 5, after the catalyst has been removed by filtration;

5% by weight of Lutensol® A 7 N (= C12-C14 ethoxylated fatty alcohol with 7 EO units)

0.5% by weight butylhydroxyanisole;

1.5% by weight lauryldimethylamine oxide.

Reference example 11

Reichert Wear Test

The well known Reichert wear tester consists of two cylinders made of stainless steel (V2A). One is used as the stationary wear member and the second cylinder as the rotary wear member operating 90 ° towards the stationary member.

The metal cylinders are washed with ethanol prior to use, and the fluid reservoir is filled with a 1% solution of the test substance in water. The second metal cylinder is rotated at least once on the motor shaft before the weight is placed on the first cylinder. After starting the rotation of the second cylinder, the noise (caused by metal / metal friction) is measured. Cylinder rotation is measured in meters of stroke. When lubrication starts (lube point), the noise level drops significantly, and the run meters are recorded. After 100 m the rotation is stopped, the metal cylinders are washed with ethanol and the wear signal of the stationary wear member is analyzed (measured in mm2). Typical products showing good lubrication have lubrication points less than 20m and less than 20mm2 wear after 100m.

As a reference it was tested, pure water with the Reichert wear tester. A lubrication point of 100 m and 43 mm2 of wear was obtained.

The polyalkylene glycol of Example 5, used as 1% by weight of the water solution, showed a lubrication point of 14 m and a 14 mm2 wear.

Example 12

Rotational tribometer test

In the rotational tribometer, a ball-bearing steel ball (AISI 52100, 12.7 mm diameter, 4.09 | jm fiber thickness) is held stationary and a steel plate rotates (152 mm x 102 mm x 0.8 mm) (velocity = 0.05 m / s), while the ball is pressed to the plate with F = 3 N. This test equipment is the most commonly used during the development of materials for tri-biological applications. and for lubricant formulations. The force, which is necessary to keep the ball stationary, gives the coefficient of static friction (jH) as well as the coefficient of sliding friction (jG). The test substance is poured onto the plate to form a thin film prior to the start of the measurement.

The following data were obtained:

polyalkylene glycol prepared as described in example 5:

jH: 13

jG: 12

mineral oil (IP 26/30 H, H&R WASAG AG, Salzbergen, Germany):

jH: 16

jG: 14

The results show that the polyalkylene glycol described is superior to mineral oil and has lower coefficients of friction.

Claims (9)

1. A functional fluid comprising a) 25-55% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g; b) 35-65% by weight water; c) 5-26% by weight of metal passivators and corrosion inhibitors such as tolyltriazole, benzotriazole, organic acids, esters of these, nitrogen-, phosphorus- and sulfur-containing compounds, alkyl and aryl phosphites; d) 0-5% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example butylated hydroxytoluene; e) 0-5% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, alkyl and aryl phosphates and carboxylic acids; f) 0-5% by weight of other additives such as dispersants, antifoams and stabilizers; wherein the functional fluid is a water soluble metal working fluid with low inhalation toxicity. 2. A functional fluid comprising a) 75-98% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g; b) 0-5% by weight of metal passivators such as tolyltriazole, benzothiazole and benzotriazole; c) 0-5% by weight of antioxidants such as dialkylthiopropionates, organic amines and hindered phenols, for example dilaurylthiopropionate, dioctyldiphenylamine, phenylnaphthylamine, phenothiazine and butylated hydroxytoluene; d) 0-5% by weight of corrosion inhibitors such as organic acids, esters of these, compounds containing nitrogen-, phosphorus- and sulfur, derivatives of succinic acid, 4-nonylphenoxyacetic acid, alkyl and aryl phosphites; e) 0-5% by weight of antiwear and extreme pressure additives such as dithiophosphates, amine phosphates, phosphorothionates, carbamates, alkyl and aryl phosphates; f) 0-5% by weight of other additives such as dispersants, antifoam agents and stabilizers; wherein the functional fluid is a compressor lubricant with low inhalation toxicity comprising. 3. A functional fluid comprising a) 5-35% by weight of a copolymer obtained by copolymerizing ethylene oxide, propylene oxide and / or butylene oxide with a monool or diol initiator, said copolymer having a lower degree of unsaturation of approximately 0.01 meq / g; b) 65-95% by weight of water; c) 0-5% by weight of corrosion inhibitors such as organic acids, alkyl amines, esters thereof, nitrogen-, phosphorus and sulfur-containing compounds, and derivatives of succinic acid; d) 0-5% by weight of other additives such as dispersants, antifoams and stabilizers; wherein the functional fluid is a quenching agent with low inhalation toxicity. 4. The functional fluid of any of claims 1 to 3 wherein the LC50 value of the copolymer is greater than 1000 mg / m3, determined according to method 403 of the OECD Guideline. 5. The functional fluid of any of claims 1 to 3 wherein the copolymer is an ethylene oxide / propylene oxide copolymer. 6. The functional fluid of any of claims 1 to 3 wherein the initiator is a monool initiator selected from the group consisting of C1-C18 monoalcohols or polyoxyalkylene monoethers of C1-C18 monoalcohols containing 1 to 20 oxyalkylene units. 7. The functional fluid of any of claims 1 to 3 wherein the monool initiator is n-butanol. 8. The functional fluid of any one of claims 1 to 3 wherein the copolymer has an average molecular weight Mw from 800 to 20000 g / mol. 9. The functional fluid of any of claims 1 to 3 wherein the copolymer is obtained in the presence of a DMC catalyst.